Method for permanently reshaping keratin fibers comprising applying a poorly concentrated reducing composition and intermediate drying

ABSTRACT

The present disclosure relates to a method for permanently reshaping the keratin fibers, for example for permanently reshaping the hair, comprising:
         mechanically setting the keratin fibers under tension by winding the same around at least one mechanical tensioning device, said at least one device being flexible and closable upon itself, so as to form a curl,   applying onto the keratin fibers at least one reducing composition, so as to reduce the keratin disulfide bonds,   an optional rinsing,   drying the keratin fibers, and   applying at least one oxidizin composition, to reform said bonds.

This application claims benefit of U.S. Provisional Application No.60/907,307, filed Mar. 28, 2007, the contents of which are incorporatedherein by reference. This application also claims benefit of priorityunder 35 U.S.C. § 119 to French Patent Application No. FR 0655915, filedDec. 22, 2006, the contents of which are also incorporated herein byreference.

Disclosed herein is a method for permanently reshaping hair comprising ahair drying step between applying at least one reducing composition tothe hair and applying at least one oxidizing composition to the hair,this method being associated with the use of a device for mechanicallysetting the hair under tension, said device being flexible and closableupon itself, so as to form a curl.

The most usual art to obtain a permanent deformation of the haircomprises, in a first step, opening the keratin S—S disulfide bonds(cystine) with a composition comprising a suitable reducing agent(reducing step) then, once the thus treated hair has been rinsed,generally with water, reforming in a second step said disulfide bonds,by applying onto the hair which has been placed beforehand undertension, using curlers for example, an oxidizing composition (oxidizingstep, also called fixing step) so as to give the hair the expected formin the end. This method thus makes it possible to wave the hair (permmethod). The new shape that has been imposed to the hair by means of achemical treatment, such as hereabove, may be temporally substantiallylong-lasting and may resist washing operations with water or shampoo, asopposed to the usual simple methods for temporarily reshaping the hairusing a set.

Tension provided by curlers often allows one to provide a hair liftingat the root level leading to an expansion of the hair volume, thusinherently causing a curling of the whole hair strand.

However, some people may like to increase their hair volume, withoutobtaining frizzy hair. In other words, while it may be desirable to beable to produce a hair volume expansion, there is also a need forreplacing the curliness along the whole hair strand inherent in the hairshaping traditional methods, which are often substantiallybidimensional, with full three-dimensional spiral-shaped curls.

There is hence a need for a method for permanently reshaping the hairthat would be able to durably provide a hair volume expansion by liftingthe same at the root level, together with three-dimensional formedcurls.

While the hair setting using a round iron makes it possible to obtainthis type of spiral-shaped full curls, these often disappear as soon asthe first shampoo is done, because of the breaking of the created ionicand saline bonds.

Using usual rollers during the traditional hair shaping method is notsatisfying either, since this method type may lead to a temporally poorquality hair fixing and does not allow three-dimensional shaped curls tobe formed. No one of the described methods does thus lead to a fullysatisfying permanently reshaping method as regards the hereabovementioned problems.

The inventors have found, surprisingly, that the previously mentioneddrawbacks of the prior art may be solved thanks to a method forpermanently reshaping the keratin fibers, comprising drying the keratinfibers between applying at least one reducing composition and applyingat least one oxidation fixing composition, such method being associatedwith the use of devices for mechanically setting the keratin fibersunder tension, said devices being flexible and closable upon themselvesso as to form a curl. Thus, disclosed herein is a method for permanentlyreshaping the keratin fibers, such as for permanently reshaping thehair, comprising:

mechanically setting the keratin fibers under tension by winding thesame around a mechanical tensioning device, said device being flexibleand closable upon itself, so as to form a curl;

applying onto the keratin fibers at least one reducing composition, soas to reduce the keratin disulfide bonds; optionally rinsing the keratinfibers,

drying the keratin fibers; and

applying onto the keratin fibers at least one oxidizing composition.

The hereabove mentioned method can allow one to produce, rapidly anddurably, a keratin fiber volume expansion, such as a hair volumeexpansion, by lifting the keratin fibers at the root level, togetherwith three-dimensional formed curls.

As used herein, “flexible” means a device comprising for all or part ofits whole length a material that is sufficiently supple for said devicebe able to be folded upon itself and form a curl. Such material may, forexample, be a plastic malleable, molded, aerated or foamed material, ametallized or non metallized paper, a fibrous material, such as cord andtwine, or a non woven material.

As used herein, “closable” means a device which makes it possible toform a curl along at least one part of its length.

In at least one embodiment, the mechanical tensioning device is a curleror a suitable curlpaper. In another embodiment, the curler used duringhair tensioning is a tulip-type curler comprising a body-formingextended rod, ending at one end thereof with a head comprising at leastone hole. The curler body is made in a flexible material, so that itsfree end may be introduced into the at least one head hole and befixedly maintained there by an elastic clamping. A curler of thehereabove type, suitable for implementing the method of the disclosureis, for example, described in the French Patent Application No. FR 2 602650.

Using at least one tulip-type curler can make it possible to control thetension applied onto the hair and thus to give a rounded form to hairstrands during the treatment time, without excessively pulling the hair,as opposed to what often happens with most cylindrical curlers. Using atleast one tulip-type curler in the context of the method disclosedherein also may allow one to avoid the problematic marks often formed atthe hair root and to obtain three-dimensional, spiral-shaped curls, theamplitude of which may vary depending on the amount of tulip-typecurlers used, rather than the bidimensional waving of the hair strandswhich is often produced with cylindrical curlers. The winding of the atleast one curler may be conducted either on the whole hair length, or onhalf-length for long-length hair.

Depending on the hair shape and on the expected curl volume, the windingup is carried out on more or less thick hair strands.

To obtain a result similar to that described hereabove, at least onecurlpaper may be used instead of the at least one tulip-type curler,provided that the hair be wound on the at least one curlpaper and thiscurlpaper is folded upon itself to form a curl.

The at least one reducing composition used in the method disclosedherein can comprise, in a cosmetically acceptable medium, at least onereducing agent chosen from sulfites, bisulfites, thiols and phosphines.

Suitable examples of sulfites and bisulfites to be used include, but arenot limited to, alkaline metal or alkaline-earth metal, or ammoniumsulfites or bisulfites, and sodium, potassium or monoethanol aminesulfite or bisulfite.

In at least one embodiment, the at least one thiol used as the at leastone reducing agent in the reducing composition is chosen from cysteineand derivatives thereof, such as N-acetylcysteine, cysteamine andderivatives thereof, such as from C1-C4 acyl derivatives thereof, suchas N-acetyl cysteamine and N-propionyl cysteamine; thiolactic acid andesters thereof, such as glycerol monothiolactate, thioglycolic acid andesters thereof, such as glycerol or glycol monothioglycolate, andthioglycerol; and mixtures thereof.

Suitable examples of thiols to be used in the at least one reducingcomposition used according to the disclosure further include, but arenot limited to, sugar N-mercapto alkyl amides, such asN-(mercapto-2-ethyl)gluconamide, β-mercaptopropionic acid andderivatives thereof; thiomalic acid; pantheteine;N-(mercaptoalkyl)ω-hydroxyalkyl amides, such as those described in theEuropean Patent Application Publication No. EP-A-354 835 and N-mono- orN,N-dialkylmercapto 4-butyramides, such as those described in theEuropean Patent Application Publication No. EP-A-368 763;aminomercaptoalkyl amides, such as those described in the EuropeanPatent Application Publication No. EP-A-432 000 andalkylaminomercaptoalkylamides, such as those described in the EuropeanPatent Application Publication No. EP-A-514 282; and (2/3) hydroxy-2propyl thioglycolate and hydroxy-2 methyl-1 ethyl thioglycolate-basedmixture (67/33) described in the French Patent Application PublicationNo. FR-A-2 679 448.

In at least one embodiment, cysteine is used.

The at least one reducing agent can be present in an amount for eachranging from 0.5 to 10% relative to the total weight of the reducingcomposition, such as from 1 to 8% or from 2 to 7% by weight.

According to at least one embodiment, the at least one reducingcomposition is allowed to react for a period of time ranging from 1 to50 minutes, for example for from 1 to 30 minutes.

During or after application of the at least one reducing composition,the keratin fibers are submitted to a thermal treatment by heating, forexample to a temperature ranging from 30 to 250° C. for part of or allthe reaction time defined hereabove. In practice, this operation may,for example, be conducted by using a hood hair dryer, a hair dryer, around iron or a flat iron, an IR-emitting device and other heatingdevices, and in some cases under a plastic film.

The pH value of the reducing composition of the disclosure ranges, forexample, from 7.5 to 11, such as from 8 to 9.5.

The pH value of the reducing composition of the disclosure may beobtained and/or adjusted by adding at least one alkaline agent, such asfor example ammonia, monoethanol amine, diethanol amine, triethanolamine, isopropanol amine, 2-methyl-2-amino-1-propanol,propanediamine-1,3, alkaline or ammonium carbonate or bicarbonate,sodium carbonate and bicarbonate, an organic carbonate, such asguanidine carbonate, or mixtures thereof; or at least one acidifyingagent, such as for example hydrochloric acid, acetic acid, lactic acid,boric acid, citric acid and/or phosphoric acid.

For improving the cosmetic properties of the hair fibers or to reduce orprevent their damage, the at least one reducing composition used in themethod of the disclosure may also comprise at least one cosmetic activeagent.

The at least one cosmetic active agent can be chosen from volatile ornon volatile, linear or cyclic, amine-type or not, silicones; cationic,anionic, non ionic or amphoteric polymers, peptides and derivativesthereof; protein hydrolyzates; synthetic or natural waxes; and fattyalcohols, swelling agents and penetrating agents or agents intended toimprove the efficiency of the at least one reducing agent; and otheractive compounds, such as anionic, cationic, non ionic, amphoteric orzwitterionic surfactants; agents for combating hair loss; anti-dandruffagents, associative-type or not; natural or synthetic thickeners;suspending agents; sequestering agents; opacifying agents; dyes;sunscreen agents; fillers; vitamins or provitamins; mineral, vegetableor synthetic oils; fragrances; preserving agents; stabilizers; andmixtures thereof.

In at least one embodiment, the at least one reducing compositioncomprises at least one cationic polymer and/or at least one silicone.

As used herein, a “cationic polymer” means any polymer comprisingcationic groups or groups ionizable to cationic groups.

In one embodiment, the at least one cationic polymer is chosen fromthose comprising units containing primary, secondary, tertiary and/orquaternary amine groups, that either may belong to the polymer mainchain, or are carried by a side substituent that is directly bound toit.

The at least one cationic polymer that can be used has generally anumber average molecular weight ranging from 500 to 5×10⁶, for examplefrom 103 to 3×10⁶.

In at least one embodiment, the at least one cationic polymer is chosenfrom polyamine, polyaminoamide and quaternary polyammonium typepolymers.

These are known products. They are, for example, described in the FrenchPatent Nos. 2 505 348 and 2 542 997. Examples of said cationic polymersinclude, but are not limited to:

(1) Homopolymers or copolymers derived from acrylic or methacrylicesters or amides and comprising at least one unit of following formulae(I), (II), (III) or (IV):

wherein:

R₃, being the same or different, is chosen from hydrogen atoms and CH₃radicals;

A, being the same or different, is chosen from linear or branched alkylgroups comprising from 1 to 6 carbon atoms, such as 2 or 3 carbon atoms,and hydroxyalkyl groups comprising from 1 to 4 carbon atoms;

R₄, R₅, R₆, being the same or different, are chosen from alkyl groupscomprising from 1 to 18 carbon atoms and benzyl radicals, for examplealkyl groups comprising from 1 to 6 carbon atoms;

R₁ and R₂, being the same or different, are chosen from hydrogen atomsand alkyl groups comprising from 1 to 6 carbon atoms, for example methylor ethyl groups;

An anion X is optionally present, and when present is an anion derivedfrom a mineral or an organic acid, such as a methosulfate anion or ahalide, such as chloride or bromide.

Polymers of family (1) may further comprise at least one unit derivedfrom comonomers that may be chosen from acrylamides, methacrylamides,diacetone acrylamides, acrylamides and methacrylamides substituted on anitrogen atom with lower from (C₁-C₄)alkyl groups, acrylic ormethacrylic acids or esters thereof, vinyl lactames, such as vinylpyrrolidone or vinyl caprolactame, and vinyl esters.

Thus, these polymers of family (1) include, for example, but are notlimited to:

-   -   copolymers of acrylamide and dimethyl aminoethyl methacrylate        quaternized with dimethyl sulfate or dimethyl halide, such as        the one marketed under the name HERCOFLOC by HERCULES;    -   copolymers of acrylamide and methacryloyloxyethyl        trimethylammonium chloride described, for example, in European        Patent Application No. A-080976, such as products marketed under        the name BINA QUAT P 100 by CIBA GEIGY;    -   copolymers of acrylamide and methacryloyloxyethyl        trimethylammonium methosulfate, such as products marketed under        the name RETEN by HERCULES;    -   copolymers of vinyl pyrrolidone and dialkylaminoalkyl acrylate        or methacrylate, quaternized or not, such as products marketed        under the name “GAFQUAT” by ISP, for example “GAFQUAT 734” or        “GAFQUAT 755”, or products called “COPOLYMER 845, 958 and 937”.        These polymers are also described in detail in French Patent        Nos. 2 077 143 and 2 393 573;    -   terpolymers of dimethylaminoethyl methacrylate, vinyl        caprolactame and vinyl pyrrolidone, such as the product marketed        under the name GAFFIX VC 713 by ISP;    -   copolymers of vinyl pyrrolidone and methacrylamidopropyl        dimethyl amine marketed, for example, under the trade name        STYLEZE CC 10 by ISP; and quaternized copolymers of vinyl        pyrrolidone and dimethylaminopropyl methacrylamide, such as the        product marketed under the name “GAFQUAT HS 100” by ISP.

(2) Cellulose ether derivatives comprising quaternary ammonium groups,such as those described in the French Patent No. 1 492 597, and forinstance, polymers marketed under the trade names “JR” (JR 400, JR 125,JR 30M) or “LR” (LR 400, LR 30M) by Union Carbide Corporation. Thesepolymers are also defined in the CTFA dictionary as beinghydroxyethylcellulose quaternary ammonium compounds having reacted withan epoxide substituted with a trimethylammonium group.

(3) Cationic cellulose derivatives, such as copolymers of cellulose orcellulose derivatives graft with a quaternary ammonium hydrosolublemonomer, and described, for example, in U.S. Pat. No. 4,131,576, such ashydroxyalkyl celluloses, for example hydroxymethyl-, hydroxyethyl- orhydroxypropyl celluloses graft, for example, with a methacryloylethyltrimethylammonium, methacryImidopropyl trimethylammonium, or a dimethyldiallylammonium salt.

The products marketed corresponding to this definition include, but arenot limited to, products marketed under the name “Celquat L 200” and“Celquat H 100” by National Starch.

(4) Cationic polysaccharides, such as those described in U.S. Pat. Nos.3,589,578 and 4,031,307, such as guar gums comprising trialkylammoniumcationic groups. Guar gums modified with a 2,3-epoxypropyltrimethylammonium (e.g. chloride) salt may be used, for example.

Such products are marketed, for example, under the trade names JAGUARC13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by MEYHALL.

(5) Polymers comprising piperazinyl units and alkylene orhydroxyalkylene divalent radicals with straight or branched chains,optionally interrupted with oxygen, sulfur, nitrogen atoms or witharomatic or heterocyclic rings, as well as oxidation products and/orquaternization products of these polymers. Such polymers are, forexample, described in French Patent Nos. 2 162 025 and 2 280 361.

(6) Water-soluble polyaminoamides such as those prepared bypolycondensing an acidic compound with a polyamine; thesepolyaminoamides may be crosslinked with an epihalohydrine, a diepoxide,a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative,a bis-halohydrine, a bis-azetidinium, a bis-haloacyidiamine, an alkylbis-halide or with an oligomer resulting from the reaction of abifunctional compound reactive against a bis-halohydrine, abis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, anepilhalohydrine, a diepoxide or a bis-unsaturated derivative; thecrosslinking agent being used in amounts ranging from 0.025 to 0.35 moleper amine group of the polyaminoamide; these polyaminoamides may bealkylated or, in the event they have at least one tertiary aminefunctional group, quaternized. Such polymers are, for example, describedin French Patent Nos. 2 252 840 and 2 368 508.

(7) Polyaminoamide derivatives resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids, followed with analkylation with bifunctional agents. Polymers of adipic acid anddialkylaminohydroxyalkyl dialkylene triamine may be mentioned, forexample, wherein the alkyl radical comprises from 1 to 4 carbon atomsand is chosen from methyl, ethyl and propyl groups. Such polymers are,for example, described in French Patent No. 1 583 363.

Examples of these derivatives include, but are not limited to, polymersof adipic acid, dimethylaminohydroxypropyl and diethylene triaminemarketed under the name “Cartaretine F, F4 or F8” by Sandoz.

(8) Polymers obtained by reacting a polyalkylene polyamine comprisingtwo primary amine groups and at least one secondary amine group with adicarboxylic acid chosen from diglycolic acid and saturated aliphaticdicarboxylic acids comprising from 3 to 8 carbon atoms. The molar ratioof the polyalkylene polyamine to the dicarboxylic acid ranges from 0.8:1to 1.4:1. The thus resulting polyaminoamide is reacted withepichlorhydrine according to a molar ratio of epichlorhydrine to the atleast one secondary amine group of the polyaminoamide ranging from 0.5:1to 1.8:1. Such polymers are, for example, described in U.S. Pat. Nos.3,227,615 and 2,961,347.

Polymers of this type are, for example, marketed under the trade name“Hercosett 57” by Hercules Inc. or under the trade name “PD 170” or“Delsette 101” by Hercules in the case of the copolymer of adipic acid,epoxypropyl and diethylene triamine.

(9) Cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium,such as homopolymers or copolymers comprising as a main substituent ofthe chain units of formulae (V) or (VI):

wherein k and t are 0 or 1, the sum k+t being equal to 1; R₉ is chosenfrom hydrogen atoms and methyl radicals; R₇ and R₈, independently fromeach other, are chosen from alkyl groups comprising from 1 to 22 carbonatoms, hydroxyalkyl groups wherein the alkyl group comprises from 1 to 5carbon atoms, and lower amido(C₁-C₄)alkyl groups, or R₇ and R₈ mayrepresent together with the nitrogen atom to which they are bound,heterocyclic groups, such as piperidinyl or morpholinyl; in oneembodiment, R₇ and R₈ independently from each other represent an alkylgroup comprising from 1 to 4 carbon atoms; Y⁻ is an anion, such asbromide, chloride, acetate, borate, citrate, tartrate, bisulfate,bisulfite, sulfate, phosphate. These polymers are, for example,described in French Patent No. 2 080 759 and in related French PatentNo. 2 190 406.

The previously defined polymers also encompass, for example, thedimethyldiallylammonium chloride homopolymer marketed under the name“Merquat 100” by Calgon (as well as its homologues having a low weightaverage molecular weight) and copolymers of diallyldimethylammoniumchloride and acrylamide marketed under the trade name “MERQUAT 550”.

(10) Quaternary diammonium polymers comprising repeating units offormula (VII):

R₁₀, R₁₁, R₁₂ and R₁₃, being the same or different, are chosen fromaliphatic, alicyclic, or aryl aliphatic radicals comprising from 1 to 20carbon atoms or lower hydroxyalkyl aliphatic radicals, or R₁₀, R₁₁, R₁₂and R₁₃, taken together or separately, form together with the nitrogenatoms to which they are bound heterocycles optionally comprising asecond heteroatom different from nitrogen, or R₁₀, R₁₁, R₁₂ and R₁₃represent a linear or branched, from C₁-C₆ alkyl radical, substitutedwith a nitrile, ester, acyl, amide or —CO—O—R₁₄-D or —CO—NH—R₁₄-D group,where R₁₄ is an alkylene and D a quaternary ammonium group;

A1 and B1 represent polymethylene groups comprising from 2 to 20 carbonatoms that may be linear or branched, saturated or unsaturated, and thatmay contain, bound to or inserted within the main chain, at least onearomatic ring, or at least one oxygen or sulfur atom, or sulfoxide,sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium,ureido, amide or ester group, and

X⁻ represents an anion derived from a mineral or an organic acid;

A₁, R₁₀ and R₁₂ may form together with the two nitrogen atoms to whichthey are bound a piperazine ring; moreover, if A1 represents a linear orbranched, saturated or unsaturated alkylene or hydroxyalkylene radical,B1 may also represent a —(CH₂)n-CO-D-OC—(CH₂)n- group, wherein D ischosen from:

a) glycol residues of formula: —O-Z-O—, where Z represents a linear orbranched hydrocarbon radical or a group having one of the followingformulae:

—(CH₂—CH₂—O)x-CH₂—CH₂— and

—[CH₂—CH(CH₃)—O]y-CH₂—CH(CH₃)—

wherein x and y represent an integer ranging from 1 to 4 correspondingto a defined and unique polymerization degree, or any number rangingfrom 1 to 4 corresponding to a medium polymerization degree;

b) bis-secondary diamine residues, such as a piperazine derivative;

c) bis-primary diamine residues of formula: —NH—Y—NH—, wherein Yrepresents a linear or branched hydrocarbon radical, or the bivalentradical

—CH₂—CH₂—S—S—CH₂—CH₂—; and

d) ureylene groups of formula: —NH—CO—NH—.

In at least one embodiment, X⁻ is an anion chosen from chloride andbromide.

These polymers have a number average molecular weight generally rangingfrom 1000 to 100,000.

Such polymers are, for example, described in French Patent Nos. 2 320330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 as well as in theU.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462,2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904,4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.

In one embodiment, such polymers that may be used comprise repeatingunits of formula (VIII):

wherein R₁₀, R₁₁, R₁₂ and R₁₃, being the same or different, representalkyl or hydroxyalkyl radicals comprising from 1 to 4 carbon atoms, nand p are integers ranging from 2 to 20 and X⁻ is an anion derived froma mineral or an organic acid. Hexadimethrine chloride (INCI name),marketed by CHIMEX under the reference MEXOMERE PO maybe mentioned as anon-limiting example;

(11) Quaternary polyammonium compounds comprising repeating units offormula (IX):

wherein p represents an integer ranging from 1 to 6, D may be zero ormay represent a —(CH₂)_(r)—CO— group, wherein r represents a numberequal to 4 or 7, and X⁻ is an anion;

Such polymers may be prepared according to methods described in the U.S.Pat. Nos. 4,157,388, 4,702,906, and 4,719,282. They are, for example,described in the European Patent Application No. EP-A-122 324.

Suitable examples thereof include, but are not limited to, “Mirapol A15”, “Mirapol AD1”, “Mirapol AZ1” and “Mirapol 175” products sold byMiranol.

(12) Quaternary polymers of vinyl pyrrolidone and vinyl imidazole, suchas for example the products marketed under the trade names Luviquat FC905, FC 550 and FC 370 by BASF.

(13) Polyamines, such as Polyquart H sold by HENKEL, under the reference“POLYETHYLENE GLYCOL (15) TALLOW POLYAMINE” in the CTFA dictionary.

(14) Crosslinked polymers of methacryloyloxyalkyl(C₁-C₄)trialkyl(C₁-C₄)ammonium salts, such as polymers obtained byhomopolymerizing dimethylaminoethyl methacrylate quaternized with methylchloride, or by copolymerizing acrylamide with dimethylaminoethylmethacrylate quaternized with methyl chloride, where the homo- orcopolymerization are followed with a crosslinking with an olefinicallyunsaturated compound, for example methylene bis acrylamide. In oneembodiment, a crosslinked copolymer of acrylamide andmethacryloyloxyethyl trimethylammonium chloride (20:80 by weight) may beused in the form of a dispersion comprising 50% by weight of saidcopolymer in mineral oil. Such dispersion is marketed, for example,under the trade name “SALCARE® SC 92” by ALLIED COLLOIDS. A crosslinkedhomopolymer of methacryloyloxyethyl trimethylammonium chloride may alsobe used, comprising about 50% by weight of said homopolymer in mineraloil or in a liquid ester. Such dispersions are marketed, for example,under the trade names “SALCARE®) SC 95” and “SALCARE® SC 96” by ALLIEDCOLLOIDS.

Non-limiting examples of other cationic polymers to be suitably used inthe context of the present disclosure are polyalkylene imines, such aspolyethylene imines, polymers comprising vinyl pyridine orvinylpyridinium units, condensates of polyamines and epichlorhydrine,quaternary polyureylenes and chitin derivatives.

In at least one embodiment, the cationic polymer that is used in thecontext of the present disclosure, is a cationic polymer belonging tofamily (10) and, for example, hexadimethrine chloride (INCI name),marketed by CHIMEX under the reference MEXOMERE PO.

The cationic polymer content in the composition of the disclosure mayvary from 0.01 to 10% by weight relative to the total weight of thecomposition, such as from 0.05 to 5% or from 0.1 to 3%.

As discussed above, the at least one cosmetic active agent that may beused in the composition of the disclosure may also be chosen fromsilicones.

In one embodiment, silicones that are optionally present in the reducingcomposition of the disclosure are polyorganosiloxanes which are notsoluble in said composition and may come as oils, waxes, resins or gums.

Organopolysiloxanes are defined in more detail by Walter NOLL in“Chemistry and Technology of Silicones” (1968) Academie Press.

The at least one silicone may be volatile or not.

In at least one embodiment, when they are volatile, the at least onesilicone is chosen from those having a boiling point ranging from 60° C.to 260° C., and from:

cyclic silicones comprising from 3 to 7 silicon atoms, for example 4 or5.

Suitable non-limiting examples thereof includeoctamethylcyclotetrasiloxane marketed, for example, under the tradenames “VOLATILE SILICONE 7207” by UNION CARBIDE or “SILBIONE 70045 V 2”by RHONE POULENC, decamethylcyclopentasiloxane marketed under the tradename “VOLATILE SILICONE 7158” by UNION CARBIDE or “SILBIONE 70045 V 5”by RHONE POULENC, and mixtures thereof.

Cyclocopolymers of the dimethyl siloxane and methylalkyl siloxane typemay also be used, such as “SILICONE VOLATILE FZ 3109” marketed by UNIONCARBIDE, having following chemical structure (X):

wherein “avec” means “with.”

Mixtures of cyclic silicones with organic compounds derived from siliconmay also be used, such as the octamethyl cyclotetrasiloxane andtetratrimethylsilyl pentaerythritol mixture (50:50) and the octamethylcyclotetrasiloxane andoxy-1,1′(hexa-2,2,2′,2′,3,3′-trimethylsilyloxy)bis-neopentane mixture;

(ii) linear volatile silicones comprising from 2 to 9 silicon atoms andwherein the viscosity is lower than or equal to 5·10⁻⁶ m²/s at 25° C.,for example decamethyl tetrasiloxane marketed, for example, under thetrade name “SH 200” by TORAY SILICONE. Non-limiting examples ofsilicones belonging to this class are also described in the articlepublished in Cosmetics and Toiletries, Vol. 91, Jan. 76, P. 27-32—TODD &BYERS “Volatile Silicone fluids for cosmetics.”

In one embodiment, non volatile silicones are used, such as polyalkylsiloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, gums andsilicone resins, polyorganosiloxanes modified with organofunctionalgroups, and mixtures thereof.

In another embodiment, these silicones are chosen from polyalkylsiloxanes, for example polydimethyl siloxanes with trimethylsilyl endgroups having a viscosity ranging from 5·10⁻⁶ to 2.5 m²/s at 25° C., forexample from 1·10⁻⁵ to 1 m²/s. Silicone viscosity is, for example,measured at 25° C. according to ASTM 445 standard, Appendix C.

These polyalkyl siloxanes encompass, as non limiting examples, thefollowing commercial products:

-   -   SILBIONE fluids of 47 and 70 047 series or MIRASIL fluids        marketed by RHONE POULENC, such as for example fluid 70 047 V        500 000;    -   fluids of MIRASIL series marketed by RHONE POULENC;    -   fluids of 200 series from DOW CORNING, for instance, such as        DC200 (viscosity 60,000 Cst);    -   VISCASIL fluids from GENERAL ELECTRIC and some fluids of SF (SF        96, SF 18) series from GENERAL ELECTRIC.

Dimethylsilanol end group-containing polydimethyl siloxanes may also bementioned as non-limiting examples, (called dimethiconol in the CTFAdictionary), such as fluids of 48 series from RHONE POULENC.

This polyalkyl siloxane class also includes, for example, productsmarketed under the trade names “ABIL WAX 9800 and 9801” by GOLDSCHMIDTwhich are (C₁-C₂₀) polyalkyl siloxanes.

In one embodiment, polyalkylaryl siloxanes are chosen from linear and/orbranched, polydimethyl methylphenyl siloxanes, and polydimethyl diphenylsiloxanes with a viscosity ranging from 1·10⁻⁵ to 5·10⁻² m²/s at 25° C.

Suitable non-limiting examples of such polyalkylaryl siloxanes alsoinclude products marketed under the following trade names:

-   -   SILBIONE fluids of 70 641 series from RHONE POULENC;    -   fluids of RHODORSIL 70 633 and 763 series from RHONE POULENC;    -   DOW CORNING 556 COSMETIC GRAD FLUID from DOW CORNING;    -   silicones of PK series from BAYER, such as the PK20 product;    -   silicones of PN, PH series from BAYER, such as PN1000 and PH1        000 products; and    -   some fluids of SF series from GENERAL ELECTRIC, such as SF 1023,        SF 1154, SF 1250, SF 1265.

Examples of silicone gums that may be present in the reducingcomposition of the disclosure include, but are not limited to,polydiorganosiloxanes having high number average molecular weightsranging from 200,000 to 1,000,000 used either alone or in combination ina solvent. In one embodiment, this solvent may be chosen from volatilesilicones, polydimethyl siloxanes fluids (PDMS), polyphenylmethylsiloxane fluids (PPMS), isoparaffins, polyisobutylenes, methylenechloride, pentane, dodecane, tridecanes, and mixtures thereof.

As non-limiting examples, the following products may be mentioned:

-   -   polydimethyl siloxane,    -   polydimethyl siloxane/methylvinyl siloxane gums,    -   polydimethyl siloxane/diphenyl siloxane,    -   polydimethyl siloxane/phenylmethyl siloxane, and    -   polydimethyl siloxane/diphenyl siloxane/methylvinyl siloxane.

Further non-limiting examples of products that may be used include thefollowing mixtures:

mixtures formed from end chain-hydroxylated polydimethyl siloxane(called dimethiconol according to the CTFA dictionary nomenclature) andcyclic polydimethyl siloxane (called cyclomethicone according to theCTFA dictionary nomenclature), such as the Q2 1401 product marketed byDOW CORNING;

mixtures formed from polydimethyl siloxane gum and cyclic silicone, suchas the SF 1214 Silicone Fluid from GENERAL ELECTRIC product, which is anon-limiting example of an SF 30 gum corresponding to a dimethicone,having a number average molecular weight of 500,000 solubilized in fluidSF 1202 Silicone Fluid corresponding to decamethyl cyclopentasiloxane;

mixtures of two PDMS with different viscosities, for example of a PDMSgum and a PDMS fluid, such as the SF 1236 product from GENERAL ELECTRIC,wherein SF 1236 is a mixture of an SE 30 gum as defined hereabove with aviscosity of 20 m²/s and an SF 96 fluid with a viscosity of 5·10⁻⁶ m²/s.In one embodiment, such product comprises 15% of SE 30 gum and 85% of SF96 fluid.

In one embodiment, organopolysiloxane resins optionally present in theoxidizing composition of the method of the disclosure are siloxane-basedcrosslinked systems comprising following units: R₂SiO_(2/2),R₃SiO_(1/2), RSiO_(3/2) and SiO_(4/2), wherein R is chosen fromhydrocarbon groups comprising from 1 to 16 carbon atoms and phenylgroups. In a further embodiment, R is chosen from lower C₁-C₄ alkylradicals, such as a methyl, and phenyl radicals.

Further non-limiting examples of these resins also include the productmarketed under the trade name “DOW CORNING 593” or those marketed underthe trade names “SILICONE FLUID SS 4230 and SS 4267” by GENERALELECTRIC, which are dimethyl/trimethyl siloxane-structured silicones.

In one embodiment, resins of the trimethyl siloxysilicate type marketedunder the trade names X22-4914, X21-5034 and X21-5037 by SHIN-ETSU maybe used.

Organomodified silicones optionally present in the reducing compositionof the disclosure are chosen from silicones such as previously defined,which comprise in their structure at least one organofunctional groupbound via a hydrocarbon radical.

Examples of organomodified silicones include, but are not limited to,polyorganosiloxanes comprising:

polyethyleneoxy and/or polypropyleneoxy groups optionally comprisingfrom C₆-C₂₄ alkyl groups, such as products called dimethicone copolyolmarketed by DOW CORNING under the trade name DC 1248 or SILWET L 722, L7500, L 77, L 711 fluids from UNION CARBIDE and (C₁₋₂)alkyl methiconecopolyol marketed by DOW CORNING under the trade name Q2 5200;

amine groups, substituted or not, such as the products marketed underthe trade name GP 4 Silicone Fluid and GP 7100 by GENESEE, the176-12096G products from GENERAL ELECTRIC, the KF-860, 861 and 864products from SHINETSU or the products marketed under the trade names Q28220 or DCZ-8566 and DOW CORNING 929 or 939 or DCZ-8299 or QZ7224 by DOWCORNING. In one embodiment, the substituted amine groups are chosen fromC₁-C₄ aminoalkyl groups and amino silicones comprising alkoxy groups,such as BELSIL ADM LOG 1 silicone marketed by WACKER;

thiol groups, such as the products marketed under the trade names “GP 72A” and “GP 71” from GENESEE;

alkoxyl groups, such as the product marketed under the trade name“SILICONE COPOLYMER F-755” by SWS SILICONES and ABIL WAX 2428, 2434 and2440 by GOLDSCHMIDT;

hydroxyl groups, such as hydroxyalkyl function-containingpolyorganosiloxanes described in French Patent Application No. FR-A-8516334;

acyloxyalkyl groups, such as for example polyorganosiloxanes describedin U.S. Pat. No. 4,957,732;

anionic groups of the carboxylic type, for example the productsdescribed in European Patent EP 186 507 from CHISSO CORPORATION, or ofthe alkyl carboxylic type, such as those present in the X-22-3701 Eproduct from SHIN-ETSU; 2-hydroxyalkyl sulfonate; and 2-hydroxyalkylthiosulfate, such as products marketed by GOLDSCHMIDT under the tradenames “ABIL S201” and “ABIL S255”;

hydroxyacylamino groups, such as polyorganosiloxanes described in theEuropean Patent Application No. EP 342 834, for example the Q2-8413product from DOW CORNING.

In one embodiment, the at least one silicone is an amino silicone.

As discussed above, the method of the disclosure comprises an oxidizingcomposition applying step.

The at least one oxidizing composition comprises generally at least oneoxidizing agent chosen from hydrogen peroxide, carbamide peroxide,alkaline bromates, polythionates, persalts, such as perborates,percarbonates and persulfates.

In at least one embodiment, the at least one oxidizing agent is hydrogenperoxide.

The at least one oxidizing agent is present in an amount ranging from0.1 to 10% by weight relative to the total weight of the oxidizingcomposition, for example from 0.5 to 5%.

In one embodiment, when the at least one oxidizing agent representshydrogen peroxide in aqueous solution, the at least one oxidizingcomposition used in the method of the disclosure comprises at least onehydrogen peroxide stabilizing agent.

Examples of stabilizing agents include, but are not limited to, alkalinemetal or alkaline-earth metal pyrophosphates, such as tetrasodiumpyrophosphate, alkaline metal or alkaline-earth metal stannates,phenacetine or acid and oxyquinoline salts, such as oxyquinolinesulfate. In one embodiment, at least one stannate is used alone or incombination with at least one pyrophosphate.

The at least one hydrogen peroxide stabilizing agent may be present inan amount ranging from 0.0001% to 5% by weight relative to the totalweight of the at least one oxidizing composition, for example from 0.01to 2%.

The pH value of the at least one oxidizing composition ranges from 1.5to 4.5, for example from 2 to 3.5.

In at least one embodiment, the at least one oxidizing composition isallowed to react for a period of time ranging from 2 to 30 minutes, forexample for from 2 to 15 minutes, or from 2 to 7 minutes.

In one embodiment, the method of the disclosure comprises applying ahair-care composition comprising at least one cationic polymer to thehair.

All the cationic polymers that have been described hereabove as regardsto the reducing composition may be used in the hair-care composition.

In at least one embodiment, the at least one cationic polymer that isused in the context of the present disclosure is present in the at leastone reducing composition comprising cyclopolymers, such asdimethyldiallylammonium chloride homopolymers marketed under the tradename “MERQUAT® 100” by MERCK, diquaternary ammonium polymers of formula(VIII) or of formula (IX) and MEXOMERE PO.

In at least one embodiment, the at least one silicone is WACKER BELSILADM LOG 1 silicone.

Additionally applying a hair-care composition may allow one to limit orto prevent sensibilizing the hair, which could result from the hairtreatment by the reducing agents and the oxidizing agents during theprocess for permanently reshaping the hair according to the disclosure.The hair-care composition, such as defined hereabove may also allow oneto protect the hair's artificial color

The at least one oxidizing composition and the at least one hair-carecomposition used in the method of the disclosure may also comprise atleast one cosmetic active agent, such as those previously mentioned withrespect to the at least one reducing composition.

In at least one embodiment, the vehicle for the reducing, oxidizing andhair-care compositions used in the method of the disclosure is anaqueous medium comprising water, which may additionally comprise atleast one cosmetically acceptable organic solvent, which may, forexample, include alcohols, such as ethyl alcohol, isopropyl alcohol,benzyl alcohol and phenylethyl alcohol; or polyols or polyol ethers,such as, for example, ethylene glycol monomethyl, monoethyl andmonobutyl ethers; propylene glycol or ethers thereof, such as, forexample, propylene glycol monomethylether, butylene glycol, dipropyleneglycol; as well as diethylene glycol alkyl ethers, such as for example,diethylene glycol monoethylether or monobutylether. The at least oneorganic solvent may then be present in concentrations ranging from 0.1to 20% by weight relative to the total weight of the composition, forexample from 1 to 10%.

The pH value of the reducing composition, the oxidizing compositionand/or the hair-care composition used in the method of the disclosuremay be obtained and/or adjusted by adding either at least one alkalineagent, such as for example ammonia, monoethanol amine, diethanol amine,triethanol amine, isopropanol amine, 2-methyl-2-amino-1-propanol,propanediamine-1,3, alkaline or ammonium carbonate or bicarbonate,organic carbonate, such as guanidine carbonate, or alkaline hydroxide,where all these compounds may be considered either alone or incombination; or at least one acidifying agent, such as for examplehydrochloric acid, acetic acid, lactic acid, boric acid, citric acid andphosphoric acid.

The at least one reducing composition, the at least one oxidizingcomposition and/or the at least one hair-care composition used in themethod of the disclosure may, independently from each other, be in theform of a lotion; a gel, thickened or not; a foam; or a cream.

As discussed above, the method of the disclosure comprises applying atleast one reducing composition onto the keratin fibers, for example ontothe hair, applying at least one oxidizing composition.

According to one embodiment of the disclosure, the application of the atleast one reducing composition and/or the at least one oxidizingcomposition do(es) occur under heating or is (are) immediately followedwith heating.

In one embodiment, the method of the disclosure further comprises,following the application of the reducing composition, and/or followingthe application of the at least one oxidation composition, with rinsingthe keratin fibers with water.

In one embodiment, the at least one reducing composition may also beapplied as the hair winding up is being performed. The at least onereducing composition may then be allowed to react for a time periodranging from 1 to 50 minutes, for example from 1 to 30 minutes.

It is also possible after having applied the at least one reducingcomposition, to submit the hair to a thermal treatment by heating to atemperature ranging from 30 to 250° C. for part of or all the reactiontime. In practice, this operation may, for example, be conducted byusing a hood hair dryer, a hair dryer, a round iron or a flat iron, anIR-emitting device and other heating devices, and in some cases under aplastic film.

In a further embodiment, a rinsing operation of the keratin fibers isthen optionally effected with water, and then is followed by a dryingoperation.

In at least one embodiment, the drying step is complete, and it may bedone, for example, by using a domestic hair dryer or a hood hair dryeror a heating hair cap, or be effected by carefully wringing the hairout.

In one embodiment, the at least one oxidizing composition enabling oneto reform the keratin disulfide bonds is then applied on dry hair,generally for a reaction time ranging from 2 to 30 minutes. The hair isthen rinsed off thoroughly, for example with water, then the tensioningdevices are removed.

As discussed above, the method of the disclosure may comprise applyingto the hair a hair-care composition comprising at least one cationicpolymer and/or at least one silicone, such as an amine silicone. As anexample, the hair-care composition may be applied:

prior to setting the hair under tension,

between the hair tensioning and the application of the at least onereducing composition,

after the optional rinsing with water following the application of theat least one reducing composition and before the application of the atleast one oxidizing composition, and/or

after rinsing with water following the application of the at least oneoxidizing composition.

In one embodiment, the at least one hair-care composition is appliedbefore mechanically setting the keratin fibers under tension. Thus,according to the present disclosure, mechanically setting the keratinfibers under tension may be carried out after applying at least onehair-care composition comprising at least one cationic polymer and/or atleast one silicone, such as an amino silicone.

In one embodiment, the hair-care composition application is followedwith a rinsing, such as a rinsing with water.

Also disclosed herein is a kit comprising:

tensioning devices, as previously described,

a first compartment comprising at least one cosmetic compositioncomprising at least one reducing agent, and

a second compartment comprising at least one cosmetic composition,comprising at least one oxidizing agent.

Other than in the examples, or where otherwise indicated, all numbersexpressing quantities of ingredients, reaction conditions, and so forthused in the specification and claims are to be understood as beingmodified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thespecification and attached claims are approximations that may varydepending upon the desired properties sought to be obtained by thepresent disclosure. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should be construed in light of thenumber of significant digits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosure are approximations, unless otherwiseindicated the numerical values set forth in the specific examples arereported as precisely as possible. Any numerical value, however,inherently contains certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.

By way of non-limiting illustration, concrete examples of certainembodiments of the present disclosure are given below.

EXAMPLES Example 1

A reducing composition and an oxidizing composition were prepared andimplemented a method for permanently reshaping the hair according to thedisclosure.

Formulations are as follows:

Composition Example

In the following composition examples, percentages are expressed byweight relative to the total weight of the composition.

Reducing Composition (1):

Cysteine 4% Ammonium thioglycolate in 1.5% 71% aqueous solutionMonoethanolamine 2.8% Ammonium bicarbonate 2.7% Sodiumcocoamphopropionate 1.4% Mexomer PO (60% active material) 1.6%Demineralized water qs 100% pH value 8.8

Oxidizing Composition (2)

Hydrogen peroxide 4.8% Stabilizers 0.03% Citric acid 0.1% Merquat 100(Polyquatermium 6) 1.25% Lauramine oxide 2.15% Demineralized water qs100% pH value 3

Comparative assays conducted on heads with any type of hair, i.e. Asian,Indian and Caucasian, natural or sensitized hair, were performed byapplying the hereabove described compositions, in the context of a hairreshaping method in accordance with the disclosure, as also as describedin example 2. With the method of the disclosure, better results wereobtained as regards the curl quality as compared to a traditionalprocedure. Three-dimensional curls were obtained, as well as a verynatural hair feel.

Moreover, a protecting effect on artificially colored hair was observedboth during the implementation of this method, and after, upon repeatedwashing with shampoos. In other words, the method for permanentlyreshaping the keratin fibers of the disclosure did not deteriorate theartificial hair color.

Example 2 Method for Permanently Reshaping the Hair

The hair of a model was shampooed, then rinsed off.

The whole hair was wound around tulip-type curlers.

The reducing composition 1 was applied, a plastic film was wrappedaround head. The reaction was allowed to proceed under a heating hoodhair dryer for 15 minutes.

The plastic film was removed, then the hair was rinsed while thetulip-type curlers still remained in place.

The hair was then placed under heating hood hair dryer until it wascompletely dry.

Oxidizing composition 2 was then applied and was left to stand for 5minutes.

Tulip-type curlers were then removed and the hair rinsed off.

1. A method for permanently reshaping the keratin fibers, comprising:mechanically setting the keratin fibers under tension by winding thekeratin fibers around at least one mechanical tensioning device so as toform a curl, wherein said device is flexible and closable upon itself;applying onto the keratin fibers at least one reducing composition, soas to reduce the keratin disulfide bonds, optionally rinsing the keratinfibers, drying the keratin fibers, and applying at least one oxidizingcomposition, to reform said bonds.
 2. A method according to claim 1,wherein the at least one mechanical tensioning device is at least onecurler or at least one curlpaper.
 3. A method according to claim 2,wherein the at least one curler is a tulip-type curler.
 4. A methodaccording to claim 1, wherein the at least one reducing compositioncomprises, in a cosmetically acceptable medium, at least one reducingagent chosen from sulfites, bisulfites, thiols and phosphines.
 5. Amethod according to claim 4, wherein the at least one reducing agent ischosen from L-cysteine, D-cysteine, L,D-cysteine, and the salts thereof;thiolactic acid, and the salts and esters thereof; and thioglycolicacid, and the salts and esters thereof.
 6. A method according to claim5, wherein the at least one reducing agent is present in an amountranging from 0.5 to 10% by weight, relative to the total weight of thereducing composition.
 7. A method according to claim 1, wherein the atleast one reducing composition is left to stand for a time periodranging from 1 to 50 minutes.
 8. A method according to claim 1, whereinthe pH value of the at least one reducing composition ranges from 7.5 to11.
 9. A method according to claim 1, wherein the at least one oxidizingcomposition comprises at least one oxidizing agent chosen from hydrogenperoxide, carbamide peroxide, alkaline bromates, polythionates,persalts, percarbonates and persulfates.
 10. A method according to claim9, wherein the at least one oxidizing agent is present in an amountranging from 0.1 to 10% by weight relative to the total weight of theoxidizing composition.
 11. A method according to claim 1, wherein the atleast one oxidizing composition is left to stand for a time periodranging from 2 to 30 minutes.
 12. A method according to claim 1, whereinthe pH value of the at least one oxidizing composition ranges from 1.5to 4.5.
 13. A method according to claim 1, further comprising, followingthe application of the at least one reducing composition and/orfollowing the application of the at least one oxidizing composition,with rinsing the keratin fibers with water.
 14. A method according toclaim 1, wherein the application of the at least one reducingcomposition is effected under heating or is immediately followed with aheating operation.
 15. A method according to claim 1, wherein the atleast one reducing composition and/or the at least one oxidizingcomposition are, independently of each other, in a form chosen from alotion, thickened or not thickened; a cream; a gel; and a foam.
 16. Amethod according to claim 1, wherein the mechanically setting thekeratin fibers under tension occurs after applying at least onehair-care composition which comprises at least one cationic polymerand/or at least one silicone.
 17. A method according to claim 16,wherein the application of the at least one hair-care composition isfollowed by rinsing.
 18. A multi-compartment kit, comprising: at leastone mechanical tensioning device, wherein said at least one device isflexible and closable upon itself, a first compartment comprising atleast one cosmetic composition comprising at least one reducing agent,and a second compartment comprising at least one cosmetic composition,which comprises at least one oxidizing agent.